Pyrazine bridged dicobaloximes with bis(thiophenyl)glyoxime and their molecular oxygen insertion

Switchable polymerization provides the opportunity to regulate polymer sequence and structure in ao ne-pot process from mixtures of monomers.Herein we report the use of O 2 as an external stimulus to switch the polymerization mechanism from the radical polymerization of vinyl monomers mediated by (Salen)Co III À R[ Salen = N,N'-bis(3,5-di-tertbutylsalicylidene)-1,2-cyclohexanediamine;R = alkyl] to the ring-opening copolymerization (ROCOP) of CO 2 /epoxides. Critical to this process is unprecedented monooxygen insertion into the CoÀCb ond, as rationalized by DFT calculations, leading to the formation of (Salen)Co III À O À Ra sa na ctive species to initiate ROCOP.D iblock poly(vinyl acetate)-bpolycarbonate could be obtained by ROCOP of CO 2 /epoxides with preactivation of (Salen)Co end-capped poly(vinyl acetate). Furthermore,ap oly(vinyl acetate)-b-poly(methyl acrylate)-b-polycarbonate triblock copolymer was successfully synthesized by a( Salen)cobalt-mediated sequential polymerization with an O 2 -triggered switchinaone-pot process.

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Oxygen‐Triggered Switchable Polymerization for the One‐Pot Synthesis of CO₂‐Based Block Copolymers from Monomer Mixtures

Zhao

Wang

Zhou

et al. 2019

Angewandte Chemie

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Oxygen‐Triggered Switchable Polymerization for the One‐Pot Synthesis of CO₂‐Based Block Copolymers from Monomer Mixtures

et al. 2019

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Switchable polymerization provides the opportunity to regulate polymer sequence and structure in a one‐pot process from mixtures of monomers. Herein we report the use of O2 as an external stimulus to switch the polymerization mechanism from the radical polymerization of vinyl monomers mediated by (Salen)CoIII−R [Salen=N,N′‐bis(3,5‐di‐tert‐butylsalicylidene)‐1,2‐cyclohexanediamine; R=alkyl] to the ring‐opening copolymerization (ROCOP) of CO2/epoxides. Critical to this process is unprecedented monooxygen insertion into the Co−C bond, as rationalized by DFT calculations, leading to the formation of (Salen)CoIII−O−R as an active species to initiate ROCOP. Diblock poly(vinyl acetate)‐b‐polycarbonate could be obtained by ROCOP of CO2/epoxides with preactivation of (Salen)Co end‐capped poly(vinyl acetate). Furthermore, a poly(vinyl acetate)‐b‐poly(methyl acrylate)‐b‐polycarbonate triblock copolymer was successfully synthesized by a (Salen)cobalt‐mediated sequential polymerization with an O2‐triggered switch in a one‐pot process.

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Dicobaloxime/organodicobaloximes bridged by different axial groups: synthesis, characterization, spectroscopy, and catalysis

et al. 2017

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Pyrazine bridged dicobaloximes with bis(thiophenyl)glyoxime and their molecular oxygen insertion

Cited by 6 publications

References 36 publications

Oxygen‐Triggered Switchable Polymerization for the One‐Pot Synthesis of CO₂‐Based Block Copolymers from Monomer Mixtures

Oxygen‐Triggered Switchable Polymerization for the One‐Pot Synthesis of CO₂‐Based Block Copolymers from Monomer Mixtures

Oxygen‐Triggered Switchable Polymerization for the One‐Pot Synthesis of CO₂‐Based Block Copolymers from Monomer Mixtures

Dicobaloxime/organodicobaloximes bridged by different axial groups: synthesis, characterization, spectroscopy, and catalysis

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Pyrazine bridged dicobaloximes with bis(thiophenyl)glyoxime and their molecular oxygen insertion

Cited by 6 publications

References 36 publications

Oxygen‐Triggered Switchable Polymerization for the One‐Pot Synthesis of CO2‐Based Block Copolymers from Monomer Mixtures

Oxygen‐Triggered Switchable Polymerization for the One‐Pot Synthesis of CO2‐Based Block Copolymers from Monomer Mixtures

Oxygen‐Triggered Switchable Polymerization for the One‐Pot Synthesis of CO2‐Based Block Copolymers from Monomer Mixtures

Dicobaloxime/organodicobaloximes bridged by different axial groups: synthesis, characterization, spectroscopy, and catalysis

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Product

Resources

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Oxygen‐Triggered Switchable Polymerization for the One‐Pot Synthesis of CO₂‐Based Block Copolymers from Monomer Mixtures

Oxygen‐Triggered Switchable Polymerization for the One‐Pot Synthesis of CO₂‐Based Block Copolymers from Monomer Mixtures

Oxygen‐Triggered Switchable Polymerization for the One‐Pot Synthesis of CO₂‐Based Block Copolymers from Monomer Mixtures